WO2020120393A1 - Silice précipitée pour séparateur d'accumulateur - Google Patents

Silice précipitée pour séparateur d'accumulateur Download PDF

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Publication number
WO2020120393A1
WO2020120393A1 PCT/EP2019/084215 EP2019084215W WO2020120393A1 WO 2020120393 A1 WO2020120393 A1 WO 2020120393A1 EP 2019084215 W EP2019084215 W EP 2019084215W WO 2020120393 A1 WO2020120393 A1 WO 2020120393A1
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WIPO (PCT)
Prior art keywords
precipitated silica
silica
doa
anyone
value
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PCT/EP2019/084215
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English (en)
Inventor
Jules VALENTE
Brice SCHLEGEL
Lionel BARRIQUAND
Original Assignee
Rhodia Operations
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Publication date
Application filed by Rhodia Operations filed Critical Rhodia Operations
Priority to US17/299,357 priority Critical patent/US20220021077A1/en
Priority to EP19816696.9A priority patent/EP3894354A1/fr
Publication of WO2020120393A1 publication Critical patent/WO2020120393A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to precipitated silica for use in the
  • a typical microporous battery separator precipitated silica is combined with a polyolefin, generally high molecular weight polyethylene, a process oil, and other ingredients to form a separator mixture that is extruded through a slot die to form an oil-filled sheet.
  • the oil-filled sheet is calendered to its desired thickness and profile, and the majority of the process oil is extracted.
  • the sheet is dried to form a microporous polyolefin separator, hereinafter referred to as“separator”, and it is slit into an appropriate width for a specific battery design.
  • the separator is fed to a machine that forms "envelopes" by cutting the separator material and sealing its edges such that an electrode can be inserted to form an electrode package.
  • the electrode packages are stacked such that the separator acts as a physical spacer and an electronic insulator between positive and negative electrodes.
  • An electrolyte is then introduced into the assembled battery to facilitate ionic conduction within the battery.
  • the primary purpose of the polyolefin contained in the separator is to
  • the polyolefin preferably has a molecular weight that provides sufficient molecular chain entanglement to form a microporous web with high puncture resistance.
  • Ultra-high molecular weight polyethylene is the material of choice.
  • silica The primary purpose of the silica is to increase the acid wettability of the separator web, thereby lowering the electrical resistivity of the separator. In the absence of silica, the sulfuric acid would not wet the hydrophobic polyolefin material and ion transport would not occur, resulting in an inoperative battery.
  • a polyethylene-based separator has a silica-to-polyethylene
  • silica particles are not completely broken down into their individual aggregates during the extrusion process, thereby providing insufficient silica dispersion throughout the separator web.
  • polyethylene separator would undesirably increase the electrical resistivity and/or reduce the acid wettability.
  • microporous polyolefin separator preferably a microporous polyethylene separator, having a material composition that provides good balance among mechanical resistance, dispersion of the precipitated silica in the polyolefin matrix and low electrical resistivity.
  • a dispersible precipitated silica has now been found which may be used to form battery separators of low specific resistance and good mechanical properties.
  • Object of the invention is a precipitated silica characterised by:
  • DOA oil absorption equal to or greater than 200 mL/100 g
  • the precipitated silica of the invention is characterised by a DOA oil
  • DOA oil absorption refers to the oil absorption capacity of the precipitated silica measured by using di-(2-ethylhexyl) adipate (DOA) and expressed as ml_ of oil per 100 g of S1O2.
  • the DOA oil absorption is typically equal to or greater than 205 mL/100 g, preferably equal to or greater than 210 mL/100 g.
  • the DOA oil absorption may even be equal to or greater than 215 mL/100 g, still equal to or greater than 230 mL/100 g.
  • the DOA oil absorption generally does not exceed 380 mL/100 g, even 350 mL/100 g, still 310 mL/100 g.
  • the DOA oil absorption is from 205 to 380 mL/100 g, preferably from 210 to 350 mL/100 g.
  • the oil absorption capacity of the inventive silica correlates with the ability of the silica to incorporate large amounts of the process oil during the separator sheet extrusion process.
  • absorption expressed in mL/100 g.
  • is an adimensional number. As an example if the measured value of DOA is 200 mL/100 g,
  • the median agglomerate size D50M may conveniently be equal to or less than 8.6 pm, even equal to or less than 8.5 pm. Generally the median agglomerate size D50M is not less than 3.0 pm.
  • traces of metals may be present in the silica.
  • the amount of said metals should be as low as possible as they can cause undesired side reactions during the operation of the battery and thus have a negative impact on the lifetime of the battery.
  • the precipitated silica of the invention preferably contains less than 1500 ppm of aluminium, typically less than 1000 ppm.
  • the amount of aluminium is defined as the amount by weight of aluminium metal with respect to the weight of silica.
  • the content of aluminium may be as low as 100 ppm.
  • the inventive silica also contains low amounts of other metals, in particular alkali metals.
  • the inventive silica is generally characterised by a CTAB surface area
  • CTAB surface area SCTAB of at least 90 m 2 /g, typically at least 100 m 2 /g.
  • the CTAB surface area does not exceed 250 m 2 /g, typically it does not exceed 200 m 2 /g.
  • the CTAB surface area SCTAB may be lower than 190 m 2 /g.
  • CTAB surface area SCTAB is a measure of the external specific surface area as determined by measuring the quantity of N hexadecyl- N,N,N-trimethylammonium bromide adsorbed on the silica surface at a given pH.
  • the BET surface area SBET of the inventive silica is not particularly limited.
  • BET surface area SBET is generally at least 80 m 2 /g, at least 100 m 2 /g, at least 120 m 2 /g.
  • the BET surface area SBET can be as high as 320 m 2 /g, even as high as 300 m 2 /g.
  • the precipitated silica of the invention is further characterised by a broad particle size distribution.
  • Parameter Ld determined by means of centrifugal sedimentation in a disc centrifuge (CPS) as detailed hereafter, is used to characterize the width of the particle size distribution. Ld is defined as follows:
  • dn is the diameter below which n% of the total measured mass is found.
  • Ld is an adimensional number. The width of the particle size distribution Ld is calculated on the cumulative particle size curve.
  • the term“particle” is used in the present context to refer to aggregates of primary silica particles.
  • the term“particle” is thus used as a synonym of the term“aggregate”.
  • Agglomerates are generally held together by weaker physical forces and can be separated by mechanical means, such as during a mixing operation.
  • the width of the particle size distribution Ld is at least 1.2, typically at least 1.3, preferably at least 1.4.
  • the width of the particle size distribution Ld is no more than 2.5, typically no more than 2.0.
  • inventive silica is in the range from 1.3 to 2.5, even in the range from 1.3 to 2.0.
  • the width of the particle size distribution Ld of the inventive silica can be in the range from 1.4 to 2.0, more preferably from 1.4 to 1.8.
  • the inventive silica typically has a broad pore size distribution. It has been found that the breadth of the pore size distribution, Ldp, as defined hereafter, is advantageously equal to or greater than the value of parameter B defined by equation (II):
  • inventive silica is manufactured by means of a process which
  • the inventive process comprises the steps of:
  • step (i) of the process a starting solution having a pH equal to or greater than 7.0 is provided in the reaction vessel.
  • the starting solution has a pH of between 8.0 and 13.0, especially between 8.0 and 12.0.
  • the starting solution contains at least a portion of the total amount of the silicate involved in the reaction.
  • the amount of silicate initially present in the vessel advantageously represents only a portion of the total amount of silicate involved in the reaction.
  • the starting solution is an aqueous solution, that is the solvent is water.
  • the silicate initially added to the vessel has a concentration, expressed in terms of S1O2, of between 100 g/L and 200 g/L.
  • the initial concentration of silicate (expressed in terms of S1O2) in the vessel is less than 180 g/L, even less than 170 g/L.
  • the initial concentration of silicate in the vessel is greater than 100 g/L, even at least 105 g/L. More preferably the initial concentration of silicate in the vessel is greater than 100 g/L, even at least 105 g/L, and no more than 200 g/L, even no more than 180 g/L.
  • silicate Any common form of silicate may be used in the process, such as
  • the silicate is sodium silicate.
  • sodium silicate When sodium silicate is used, it generally exhibits a ratio
  • the starting solution of step (i) may contain one or more electrolyte.
  • electrolyte is used herein in its generally accepted meaning, i.e. to identify any ionic or molecular substance which, when in solution, decomposes or dissociates to form ions or charged particles. Mention may be made of salts selected from the group consisting of the salts of alkali metals and alkaline-earth metals.
  • the electrolyte for use in the starting solution is the salt of the metal of the starting silicate and of the acid used in the process. Notable examples are for example sodium chloride in the case of the reaction of a sodium silicate with hydrochloric acid or, preferably, sodium sulfate in the case of the reaction of a sodium silicate with sulfuric acid.
  • step (i) when sodium sulfate is used as electrolyte in step (i), its
  • concentration in the starting solution is between 1 and 30 g/L, especially between 3 and 25 g/L, for example between 5 and 20 g/L.
  • step (ii) the pH of the reaction medium is reduced to a value of between 7.0 and 9.0, for example of between 7.5 and 8.5 by addition of an acid.
  • the term“acid” is used herein to refer to one or more than one acid which can be added during the course of the inventive process. Any acid may be used in the process. Use is generally made of a mineral acid, such as sulfuric acid, nitric acid or hydrochloric acid, or of an organic acid, such as acetic acid, formic acid or carbonic acid. Sulfuric acid is preferred.
  • the acid may be metered into the reaction medium in diluted or
  • the same acid at different concentrations may be used in different stages of the process.
  • a diluted acid is metered to the reaction medium in the first stages of step (ii) followed by concentrated acid.
  • step (iii) a simultaneous addition of acid and of the remaining amount of silicate is then advantageously carried out in step (iii). Said addition is carried out while maintaining the pH at a constant value of between 7.0 and 9.0, for example of between 7.5 and 8.5.
  • step (iii) On conclusion of step (iii) and in particular after the abovementioned
  • a maturing of the resulting silica suspension can be carried out, at the same pH obtained at the end of step (iii).
  • This step is generally carried out with stirring of the suspension, for example for 2 to 45 minutes, in particular for 3 to 30 minutes.
  • step (iv) a further addition of acid is carried out to obtain a pH value of between 4.0 and 6.0. A silica suspension is thus obtained.
  • the entire reaction of the silicate with the acid is generally performed at a temperature of between 70 and 96°C, in particular between 75 and 96°C.
  • the entire reaction of the silicate with the acid is performed at a constant temperature, usually of between 70 and 96°C, in particular between 75 and 96°C.
  • the temperature at the end of the reaction is higher than the temperature at the start of the reaction: thus, the temperature at the start of the reaction is preferably maintained at between 70 and 80°C and the temperature is then increased, preferably up to a value of between 85 and 96°C, at which value it is maintained up to the end of the reaction.
  • a suspension of precipitated silica is obtained, which is subsequently separated by means of a liquid/solid separation step.
  • the separation step usually comprises a filtration, followed by washing, if necessary. More than one washing step may be performed in order to reduce the residual amount of aluminium and/or other metals, such as alkali metals, in the silica.
  • the filtration is performed according to any suitable method, for example by means of a belt filter, a rotary filter, for example a vacuum filter, or, preferably a filter press.
  • the filter cake is then subjected to a liquefaction operation.
  • liquefaction is intended herein to indicate a process wherein a solid, namely the filter cake, is converted into a fluid-like mass. After the liquefaction step the filter cake is in a flowable, fluid-like form and the precipitated silica is in suspension.
  • the liquefaction step may comprise a mechanical treatment which results in a reduction of the granulometry of the silica in suspension.
  • Said mechanical treatment may be carried out by passing the filter cake through a high shear mixer, a colloidal-type mill or a ball mill.
  • the liquefaction step may be carried out by subjecting the filter cake to a chemical action, for instance by addition of water or an acid.
  • Drying may be performed according to means known in the art.
  • the drying is performed by atomization.
  • suitable atomizer in particular a turbine, nozzle, liquid pressure or two-fluid spray-dryer.
  • the process thus typically comprises a further step of filtering the
  • the inventive precipitated silica can be used in a number of applications, such as absorbent for active materials (in particular support for liquids, especially used in food, such as vitamins (vitamin E or choline chloride), as viscosity modifier, texturizing or anticaking agent.
  • absorbent for active materials in particular support for liquids, especially used in food, such as vitamins (vitamin E or choline chloride), as viscosity modifier, texturizing or anticaking agent.
  • the inventive precipitated silica finds a particularly advantageous application as filler in polymeric compositions for the preparation of battery separators.
  • a further object of the invention is a composition comprising the inventive precipitated silica and a polyolefin, in particular ultra-high molecular weight polyethylene (UHMWPE).
  • UHMWPE ultra-high molecular weight polyethylene
  • Still another object of the invention is a film or sheet, in particular a battery separator, comprising the inventive silica and ultra-high molecular weight polyethylene.
  • polyolefin means a polymer produced from a simple olefin (also called an alkene with the general formula CnHten) as a monomer.
  • Polyethylene is produced by polymerizing ethylene with or without one or more comonomers, polypropylene by polymerizing propylene with or without one or more comonomers, etc.
  • polyolefins include copolymers such as ethylene/a-olefin copolymers, propylene/a-olefin copolymers, etc.
  • Ultra-high molecular weight polyethylene can be defined as a polyethylene having an intrinsic viscosity of least about 10 dL/g. Intrinsic viscosity may be determined according to ISO standard 1628-3. In many cases the intrinsic viscosity is at least about 14 dL/g. Although there is no particular restriction on the upper limit of the intrinsic viscosity, the intrinsic viscosity is frequently in the range of from about 18 to about 39 dL/g. An intrinsic viscosity in the range of from about 20 to about 35 dL/g is most common.
  • thermoplastic polymers may also be present, as long as their presence does not materially affect the properties of the final separator material in an adverse manner.
  • additives such as minor amounts of lubricant and antioxidants, may also be present in the composition.
  • the silica to ultra-high molecular weight polyethylene weight ratio is from 1.5:1 to 3.5:1 by weight.
  • the silica may constitute from 5 % to 95 % by weight of the final separator material. Frequently, silica
  • composition may be transformed into a sheet by processing
  • a method for producing a sheet comprises the steps of: providing an ultra- high molecular weight polyethylene; providing precipitated silica; providing a processing oil; mixing ultra-high molecular weight polyethylene, precipitated silica, processing oil and optionally other ingredients together to form a mixture; extruding said mixture to form a sheet.
  • the ratio of the ultra-high molecular weight polyethylene to the processing oil is generally 1 :30 to 3:2 by weight.
  • the ratio of silica to processing oil is typically 1 :15 to 3:1 by weight.
  • the obtained sheet may be processed by means of standard techniques such as calendering, casting or blowing.
  • the sheet is preferably calendered.
  • the processing oil is extracted all or in part from said sheet to produce a matrix comprising ultra-high molecular weight and precipitated silica, the silica being distributed throughout said matrix, to produce a microporous matrix sheet.
  • the composition In an extrusion and calendering process, the composition, together with additional processing oil, is introduced to the heated barrel of a screw extruder. Attached to the extruder is a sheeting die. A continuous sheet formed by the die is forwarded without drawing to a pair of heated calender rolls acting cooperatively to form a continuous sheet of lesser thickness than the continuous sheet exiting from the die.
  • the continuous sheet is subjected to an extraction step where processing oil is partially or fully removed.
  • the extraction step may include one or more steps.
  • the continuous sheet from the calender may pass to a first extraction zone where the processing oil is substantially removed by extraction with an organic liquid which is a good solvent for the processing plasticizer, a poor solvent for the organic polymer, and more volatile than the processing oil.
  • organic extraction liquids include but are not limited to hexane, alkanes of varying chain lengths, 1 ,1 ,2-trichloroethylene,
  • the continuous sheet then passes to a second extraction zone where the residual organic extraction liquid is substantially removed by: heat, steam and/or water.
  • the continuous sheet is then passed through a forced air dryer for substantial removal of residual water and remaining residual organic extraction liquid. From the dryer the continuous sheet, which is a microporous matrix, is passed to a take-up roll.
  • the sheets conveniently have thicknesses in the order of 100 to 500 pm, preferably from 200 to 300 pm.
  • the sheets are suitable as battery separators, in particular as lead-acid battery separators.
  • the ability of silica to disperse was determined by laser diffraction using a Malvern Mastersizer 3000 on a silica suspension in water submitted to ultrasonic treatment before the measurement.
  • the ultrasonic treatment was carried out using a Vibracell generator model 75043 (750 W) using a 13 mm diameter probe.
  • the beaker was then transferred in a crystallizing dish filled with ice and water and the suspension submitted for 7 minutes to ultrasonic treatment. During this treatment, the ultrasonic probe tip was placed 1 cm from the bottom of the beaker.
  • Measurement Parameters duration of the sample measurement: 10 s; duration of blank measurement: 10 s; 3 cycles per measurement.
  • D50 M represents the median of the agglomerate size volume distribution curve.
  • DOA oil absorption capacity of silica was measured using a Brabender
  • Type E Absorptometer with using bis(2-ethylhexyl) adipate (CAS [103-23- 1]) commonly known as“DOA”.
  • the measurement was carried out as follows: 12.50 g of silica were introduced in the kneader chamber of the Brabender absorptometer. The rotation speed of the mixer blades was set to 125 rpm and the DOA was added dropwise at room temperature at a flowrate of 4 mL/min. The torque required to rotate the blades was continuously recorded. The measurement was terminated 100 seconds after the torque reached a maximum (this maximum has to be superior to 100 mNm). The experimental recording of the torque was fitted with a polynomial curve and the DOA value was taken as the first experimental point corresponding to 70% of the maximum value reached by the polynomial curve.
  • the DOA absorption capacity (in ml_/100g) of the silica was defined as : [0092] Where ⁇ ho% is the added volume of DOA when the torque value reaches 70% of the maximum value of the fitted polynomial curve and m S iiica is the introduced mass of silica (typically, 12.50 g).
  • CTAB surface area (SCTAB) values were determined according to an
  • BET surface area SBET was determined according to the Brunauer -
  • Emmett - Teller method as detailed in standard NF ISO 5794-1 , Appendix E (June 2010) with the following adjustments: the sample was pre-dried at 200°C ⁇ 10°C; the partial pressure used for the measurement P/P° was between 0.05 and 0.3.
  • utrasound system 1500 W generator type Sonics Vibracell VC1500/VCX1500 equipped with 19 mm probe (Converters: CV154+ Boosters (Part No: BFINVC21) + 19 mm Probe (Part No: 630-0208)).
  • Syringes 1.0 ml_ and 2.0 ml_ with 20ga needles; high shape glass beaker of 50 ml_ (SCFIOTT DURAN: 38 mm diameter, 78 mm high); magnetic stirrer with a stir bar of 2 cm; vessel for ice bath during sonication.
  • the measurement wavelength was set to 405 nm.
  • the following runtime options parameters were established:
  • Sample 5 1.0 mL of the 24 wt% solution + 0.8 mL of the 8 wt% solution
  • Sample 7 0.6 mL of the 24 wt% solution + 1.2 mL of the 8 wt% solution
  • Sample 8 0.4 mL of the 24 wt% solution + 1.4 mL of the 8 wt% solution
  • Sample 9 0.2 mL of the 24 wt% solution + 1.6 mL of the 8 wt% solution
  • the two solutions are homogenized in the syringe by aspiring about 0.2 mL of air followed by brief manual agitation for a few seconds, making sure not to lose any liquid.
  • the ultrasonic probe should be in proper working conditions. The following checks have to be carried out and incase of negative results a new probe should be used: visual check of the physical integrity of the end of the probe (depth of roughness less than 2 mm measured with a fine caliper); the measured d50 of commercial silica Zeosil ® 1165MP should be 93 nm ⁇ 3 nm.
  • Results The values d50, d16, d84 and Ld are on the basis of distributions drawn in a linear scale.
  • the integration of the particle size distribution function of the diameter allows obtaining a“cumulative” distribution, that is to say the total mass of particles between the minimum diameter and the diameter of interest.
  • d50 is the diameter below and above which 50% of the population by mass is found.
  • the d50 is called median size, that is diameter, of the silica aggregate.
  • d84 is the diameter below which 84% of the total mass of aggregates is measured.
  • d16 is the diameter below which 16% of the total mass of aggregates is measured.
  • Pore volume and pore size distribution were determined using a
  • Micromeritics AutoPore® IV 9520 porosimeter They were calculated by the Washburn relationship with a contact angle theta equal to 140° and a surface tension gamma equal to 485 dynes/cm. Each sample was dried before the measure in an oven at 200°C for 2 hours at atmospheric pressure. The starting weight of silica placed in the type 10 penetrometer, having an accuracy of 0.001 g, was selected for good reproducibility of the measurement, in such a way that the "stem volume used", i.e. the percentage mercury (Hg) volume consumed for filling of the penetrometer was from 40% to 80%. The penetrometer was then slowly evacuated to 50 pm of Hg and kept at this pressure for 5 min.
  • Hg percentage mercury
  • the measurement range was from 3.59 kPa (0.52 psi) to 413685 kPa (60000 psi), and at least 100 measurement points were used (19 measurement points from 3.59 kPa (0.52 psi) to 193 kPa (28 psi) with 10 seconds of equilibrium time and then 81 points from 193 kPa (28 psi) to 413685 kPa (60000 psi) with a 20 seconds equilibrium time). If appropriate, the software introduced further measurement points if the incremental intrusion volume was >0.5 mL/g. This corresponds to the first intrusion analysis. The intrusion curve was smoothed by means of the "smooth differentials" function of the equipment software.
  • Xs is the value of the diameter (nm) and Ys is value of the pore volume (mL/g).
  • Ldp is an adimensional number.
  • the pH of the reaction medium was brought to a value of 4.4 with 95 wt% sulfuric acid at a flowrate of 80.9 g/min.
  • the reaction mixture was allowed to stand for 10 minutes. A suspension of precipitated silica was obtained.
  • the suspension was filtered and washed on a filter press.
  • the filter cake thus obtained was disintegrated mechanically while adding deionized water in order to reach a silica concentration of 20 wt% in the mixture.
  • the pH of the resulting silica suspension was brought to 6.2 by the addition of 7.7 wt% sulfuric acid solution.
  • the pH of the reaction medium was brought to a value of 4.8 with 95 wt% sulfuric acid at a flowrate of 13.7 g/min.
  • the reaction mixture was allowed to stand for 10 minutes. A suspension of precipitated silica was obtained.
  • the suspension was filtered and washed on a filter press.
  • the filter cake thus obtained was disintegrated mechanically while adding deionized water in order to reach a silica concentration of 20 wt% in the mixture.
  • the pH of the resulting silica suspension was brought to 6.1 by the addition of 7.7 wt% sulfuric acid solution.
  • the pH of the reaction medium was brought to a value of 4.2 with 95 wt% sulfuric acid at a flowrate of 17.6 g/min.
  • the reaction mixture was allowed to stand for 5 minutes. A suspension of precipitated silica was obtained.
  • the suspension was filtered and washed on a filter press.
  • the filter cake thus obtained was disintegrated mechanically while adding deionized water in order to reach a silica concentration of 20 wt% in the mixture.
  • the pH of the resulting silica suspension was brought to 6.1 by the addition of 7.7 wt% sulfuric acid solution.
  • the pH of the reaction medium was brought to a value of 4.1 with 95 wt% sulfuric acid at a flowrate of 13.7 g/min.
  • the reaction mixture was allowed to stand for 5 minutes. A suspension of precipitated silica was obtained.
  • the suspension was filtered and washed on a filter press.
  • the filter cake thus obtained was disintegrated mechanically while adding deionized water in order to reach a silica concentration of 20 wt% in the mixture.
  • the pH of the resulting silica suspension was brought to 6.1 by the addition of
  • the pH of the reaction medium was brought to a value of 4.2 with 95 wt% sulfuric acid at a flowrate of 12.5 g/min.
  • the reaction mixture was allowed to stand for 10 minutes. A suspension of precipitated silica was obtained.
  • the suspension was filtered and washed on a filter press.
  • the filter cake thus obtained was disintegrated mechanically while adding deionized water in order to reach a silica concentration of 13% in the mixture.
  • the pH of the resulting silica suspension was brought to 6.2 by the addition of 7.7 wt% sulfuric acid solution.
  • Silica CS2 Tixosil® 38AB, precipitated silica commercially available from Solvay SA.
  • Silica CS3 HiSil® WB10D, precipitated silica available from PPG
  • the dry ingredients were weighed into a universal jacketed Diosna GmbH V10 mixer model. This model comes with a three-winged mixing tool on the bottom and a chopper on the side. The products were mixed without the process oil for 15 to 20 minutes at 85°C using the three-winged mixing tool at low intensity (chopper off). The process oil was weighed and stirred into a stainless steel jacketed reactor at 85°C for 15 to 20 minutes and then it was transferred to the mixer. To promote uniform dispersion in the dry materials the process oil was sprayed into the mixer using a Teejet 800050 brass spray (Spraying System Company) over a 7 minutes period. Temperature was maintained at 85°C during mixing process. Mixing was carried out using both the mixing tool on the bottom (high intensity) and the chopper (high intensity) for 30 minutes.
  • extruder from the Leistritz Company ( ZSE 18MAXX-44D) having an oil injection port in the first sector of the barrel. Process oil was injected into the extruder to reach a total oil content in the battery separator sheet of 67-70% weight.
  • the extruder was equipped with an 18 cm flat die to produce film thickness inferior to 400 pm. Temperature of the die was set at 180 °C. Head rolls were heated to 40°C and were set at a rolling speed of less than 1 m/min at 7 N tension approximately. Total feed rate was 3.6 kg/h and screw speed was 400 rpm.
  • the sheets were compression molded in a heated mold designed with a thickness of 250 pm while heat was applied.
  • the sheet was placed in the mold and heated to 160 °C without pressure for 2 minutes and then maintained for additional 2 minutes under a load of 240 bar.
  • Puncture resistance of the separator sheets was determined according to BCIS-03B standard with the use of a Lloyd-Ametek LS1 tester. Backweb thickness was measured via an Adamel-Lhomargy gauge with a precision of 0.01 mm. Three replicates were run of each experimental separator sheet. The results shown in Table 2 are the values of the puncture resistance normalized for the sheet thickness expressed in mm.
  • Alpha parameter is defined by the ratio between distilled water volume fraction accessible to the oil-free separator e ⁇ I and the isopropyl alcohol volume fraction accessible to that same oil-free separator eIRA. This value provides an indication of the ratio between the water wettable porosity in the sheet and the total porosity of the sheet (determined using isopropyl alcohol).
  • Alpha parameter is given by the formula:
  • alpha parameter e ⁇ I/eIRA
  • the distilled water volume fraction accessible to the oil-free separator was obtained with the use of a METTLER TOLEDO’S density kit scales combined with a ML 303T analytical scale.
  • a sample of diameter 40x70 mm was taken from the separator sheets as prepared above, then it was dried in a ventilated oven at 105 °C for 2 h and weighed (dry weight w1). Then, the sample was immersed into boiling distilled water for 10 to 12 minutes, then immersed into a container containing room temperature distilled water and then weighed, with the help of the density kit, in order to obtain the wet weight in distilled water (wDI2).
  • sDI (WDI3 - w1) / (WDI3 - wDl2).
  • the sample was dried again in the same conditions (ventilated oven at 105 °C for 2 h) and weighed again (w1). Then, the sample was immersed into isopropyl alcohol at room
  • eIRA (wlPA3 - w1 ) / (wlPA3 - wlPA2).
  • the separator containing the inventive silica S1 exhibits lower electrical resistivity than those containing silica CS2 and CS3.
  • the separator containing silica S1 has also a higher puncture resistance compared with the separator containing CS2 and CS3.
  • Alpha parameter provides an indication of the ability of the battery
  • inventive silica allows the preparation of separators having a slightly higher alpha parameter than the prior art silica.

Abstract

La présente invention concerne une silice précipitée appropriée pour être utilisée dans des séparateurs d'accumulateurs au plomb-acide présentant un bon équilibre entre propriétés mécaniques et résistivité électrique.
PCT/EP2019/084215 2018-12-11 2019-12-09 Silice précipitée pour séparateur d'accumulateur WO2020120393A1 (fr)

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US17/299,357 US20220021077A1 (en) 2018-12-11 2019-12-09 Precipitated silica for battery separator
EP19816696.9A EP3894354A1 (fr) 2018-12-11 2019-12-09 Silice précipitée pour séparateur d'accumulateur

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EP18306665.3 2018-12-11
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EP3992147A1 (fr) * 2020-10-28 2022-05-04 Evonik Operations GmbH Acides siliques précipités, leur procédé de fabrication et leur utilisation
RU2816976C1 (ru) * 2020-10-28 2024-04-08 Эвоник Оперейшнс Гмбх Осажденный диоксид кремния, способ его получения и его применение

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WO2008136019A2 (fr) * 2007-05-03 2008-11-13 Council Of Scientific & Industrial Research Procédé pour la préparation d'une silice précipitée finement divisée
US9334169B2 (en) * 2010-03-25 2016-05-10 Rhodia Operations Method for preparing precipitated silicas containing aluminium
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WO2022089971A1 (fr) * 2020-10-28 2022-05-05 Evonik Operations Gmbh Acides siliciques précipités, leur procédé de préparation et leur utilisation
RU2816976C1 (ru) * 2020-10-28 2024-04-08 Эвоник Оперейшнс Гмбх Осажденный диоксид кремния, способ его получения и его применение

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